Water-insoluble azo dyestuffs



Patented Mar. 7, 1939 smrss PATENT OFFICE WATER-INSOLUBLE AZO DYESTUFFS Fritz Ballauf, Cologne-Muhlheim, Germany, as-

signor to General Aniline Works, Inc., New York, N. Y., a' corporation of Delaware No Drawing. Application May 29, 1936, Serial 8 Claims.

The present invention relates to water-insoluble azo dyestufis and the fibers dyed therewith, more particularly it relates to water-insoluble azo dyestuffs which may be represented by the prob- 1 able general formula:

ZI?I-C=Y N=NR In the said formulaX stands for an oxygen atom or the imino group in which the hydrogen atom may be substituted by a hydrocarbon radical, Y

stands for an oxygen or sulfur atom, Z stands for a hydrogen atom or an alkyl group, R stands for theradical of an ice color coupling component, and wherein the naphthalene nucleus may bear substituents which do not cause solubility in water or aqueous alkalies.

My new dyestuffs are obtainable by coupling in substance or on a substratum, especially the vegetable fiber, an ice color coupling component with the diazo compound of an amine of the general formula:

ZNO=Y NH: l V wherein X, Y and Z mean the same as stated above.

Example 1 50 grams of cotton yarn are grounded for half .an hour at 30 C. in 1 literof an aqueous solution In Germany June 8, 1935 alkaline with sodium carbonate prepared in the usual manner from 1.5 grams of 2',3'-hydroxynaphthoyl 2 amino-naphthalene. Thereupon the yarn is centrifuged and developed for half an hour in 1 liter of a 40 C. diazo bath prepared according to the usual method by diazotizing 2.6 grams of the following amine:

and neutralizing with zinc oxide. Advantageously 4.3 grams of zinc sulfate are added to the diazo bath. Thereupon the dyed material is rinsed and dried. A dark blue coloration is thus obtained of very good fastness properties. The .dyestuff corresponds to the following formula:

CHaO- N-CH:

The amine of the formula:

CHaN-C=O CHa0- NCH:

can be easily prepared in the following manner:

2.7-aminonaphthol is coupled in acid medium with diazotized aniline. The dyestufi obtained is reduced in dilute acetic acid by means of zincdust. The amine can be isolated as sulfate. The amine is treated in alcohol with phosgene and the 7-hydroxy-l.2-naphthylenediamine-urea is obtained, which can be trimethylated with dimethylsulfate. 'The product thus obtained crystallizes from toluene in needles of the melting Example 2 A cotton piece material is grounded in the usual manner by a short passage through a solution containing per liter 18 grams of 2, 3-hydroxynaphthoyl 1 amino-2-methyl-4-methoxy-benzene, squeezed off and dried. Thereupon it is introduced into a diazo solution obtainable in the usual manner from 18 grams of an amine of the following formula:

Nil-0:0

N-CHa V l qHz Subsequently the material is passed either through hot water of about 70-90 C. or through a quick steam cooker, rinsed, acidified, again rinsed and after-treated in a boiling soap bath.

A navy blue of excellent fastness properties, especially to light is thus obtained. The dyestufi corresponds to the following formula:

NCHa

on GO-NHO-OCH:

The amine oi the formula:

HN-CO used above may be prepared as follows:

,B-methylnaphthylamine is coupled in acid medium with diazotized aniline and the obtained dyestufi is reduced in dilute acetic acid with zinc-dust. The 2-methylamino-a-naphthylamine is an oil, which'boils at 230 C./35 mm. When treated with phosgene in alcohol, the inner urea is obtained, which can be recrystallized in long needles from glacial acetic acid and which melts at 296 C. This compound is nitrated in glacial acetic acid. The nitration product is yellow and melts above 300 C. By reduction the amine is obtained, which in the form of the hydrochloride can be recrystallized from water. As noted above in Example 1, the corresponding thiourea can be obtained by substituting the carbon disulfide for phosgene.

In an analogous manner there are obtained on applying one of the methods described in the preceding examples by a combination of 2 ,3 -hydroxynaphthoylaniline with 7 IVE-0:0

wit-on;

NHa

A blue.

2,3'-l1ydroxynaphthoyl-l-amino-2-methyibenzene with a V I I OHI V N111 I .A havy blue.

2,3-hydtoxynaphthoyl-l-amino-4-methoxybenzene with V NH-C=O 2-hydroxyanthraccne-B-carboxylic acid-2'-toluidide with NHC=O with Ni.

A green. 2,3-hydroxynaphthoyl-l-amino-2,5-dimethoxybenzene with NHC 0 A reddish blue.

2 ,3-hyclroxynaphthoyl-l-aminonaphthalene with NH-C O A bluish violet.

2,3-hydroxynaphthoyl-aniline with A greenish blue. 2,3-hydroxynaphthoyl-l-aminc-naphthalene with CHz-N-'-G=O I on owt m NH; A navy blue.

ing 1.2-aminonaphthol with phosgene.

2',3'hydtoxynaphthoyl-l-amino-2,4-dimethy1benzene with CHa--NG=O CHiO 'NCHa A reddish blue.

2',3-hydroxynaphthoyl-l-amino-2-methy1-4-chlorobenzene with NHC O OHaO NCHa A greenish blue.

2',3'-l1ydroxynaphthoyl-l-amino-2-methyl-4-methoxybenzene with O HnN- C S A reddish blue;

7',8'-benzo-2',3'-hydroxycarbazoyl-l-amino-2-methyl-4-methoxybenzene with C H -N O= S CHaO CHI A dark blue;

The amine of the formula:

HN-C=O which is used in the fifth and sixth combinations in the above table may be prepared by treat- The product thus formed is nitrated in glacial acetic acid and then reduced to the amine.

I claim:

1. Water-insoluble azo dyestuifs selected from the group of compounds consisting of dyestuffs of the formula:

wherein X stands for a member selected from the group consisting of oxygen, the imino group and an imino group in which the hydrogen atom is substituted by a hydrocarbon radical, Y stands for a member selected from the group consisting of oxygen and sulfur, Z stands for a member selected from the group consisting of hydrogen and a saturated lower alkyl hydrocarbon, R stands for the radical of an ice color coupling component selected from the group consisting of arylamides of 2.3-hydroxynaphthoic acid, 2-hydroxyanthracene-3-carboxylic acid and o-hydroxybenzocarbazole-carboxylic acid, and such dyestufis substituted in the naphthalene nucleus by substituents which do not cause solubility in water and aqueous alkalies, yielding, when produced on the fiber, in general shades of good fastness to light.

2. The water-insoluble azodyestuff of the formula:

yielding, when produced on the fiber blue shades of good fastness properties.

3. The water-insoluble azodyestufi of the formula:

- CHr-NO=O on CQ-NHQ-OH;

wherein W and Z stand for a member of the group consisting of hydrogen and a saturated lower alkyl hydrocarbon, and A stands for a member of the group consisting of hydrogen and alkoxy, yielding when produced on the fiber in general shades of good fastness to light.

8. Fiber dyed with a dyestufi asclaimed in claim 7.

FRITZ BALLAUF. 

